Nucleophilic Phosphanylation of Fluoroaromatic Compounds with Carboxyl, Carboxymethyl, and Aminomethyl Functionalities − an Efficient Synthetic Route to Amphiphilic Arylphosphanes

Hingst, Martin; Tepper, Michael; Stelzer, O.

doi:10.1002/(sici)1099-0682(199801)1998:1<73::aid-ejic73>3.0.co;2-m

Cited by 50 publications

(32 citation statements)

References 39 publications

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“…We synthesized and used the adamantylidene-substituted monopentafulvene complex 1 and the readily accessible bidentate N , P ligand precursors L1 and L2 , with different substitution patterns at the phosphorus, which were synthesized according to procedures known in the literature in a slightly modified way (Scheme ). , Both ligand precursors were obtained in good yields of 60% and 87% as colorless ( L1 ) and pale yellow ( L2 ) solids, respectively. NMR data were recollected in C 6 D 6 for reasons of comparison (δ( 31 P{ 1 H}) −8.2 ppm ( L1 ), 6.7 ( L2 )).…”

Section: Resultsmentioning

confidence: 99%

Convenient Synthesis of Cationic Titanium Complexes with Tridentate Cp,N,P-Ligand Framework: FLP-Like Reactivity at the Ti–N Bond and Unexpected Ligand Hydrogenation Reaction

et al. 2018

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The convenient synthesis of cationic titanium complexes 4a,b is reported, starting from the titanium monopentafulvene complex 1 (Cp*Ti(Cl)(π-η 5 :σ-η 1 -C 5 H 4 CR 2 ; CR 2 = adamantylidene) and the bidentate P,N-ligand precursor compounds L1 and L2 (2-R 2 PC 6 H 4 CN; R = Ph, i Pr) with a nitrile functional group each and differently substituted phosphine moieties. In effect, 4a,b feature novel tridentate Cp,N,P-ligand systems, which were introduced directly into the coordination sphere of the titanium in conclusive two-step syntheses. Complexes 4a,b react under mild conditions with acetone and phenylacetylene selectively at the Ti−N bond in a FLP-like manner to give the corresponding complexes 5a,b and 6a,b via protonation of the nitrogen and addition of the anionic enolate and acetylide moieties to the titanium. Addition of dihydrogen to a solution of 4b at room temperature results in an unexpected hydrogenation reaction of the CN bond of the ancillary Cp,N,Pligand framework to yield complex 7b. In order to obtain further insight into the ligand design with respect to enabling subsequent reactions, another cationic titanium complex 10 was prepared with a bidentate Cp,N-ligand framework bearing no phosphine functional group, starting from 1 and 4-chlorobenzonitrile. 10 does not react with acetone, phenylacetylene, or dihydrogen, and consequently only 10 could be reisolated, even under harsher reaction conditions, showing that the phosphorus donor side is mandatory for subsequent reactions in a FLP-like manner.

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Section: Resultsmentioning

confidence: 99%

Convenient Synthesis of Cationic Titanium Complexes with Tridentate Cp,N,P-Ligand Framework: FLP-Like Reactivity at the Ti–N Bond and Unexpected Ligand Hydrogenation Reaction

et al. 2018

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“…( 1), (1) the fluorine compound can be isolated as a viscous oil in quantitative yield from the cross-coupling reaction 26,27 of 1-bromo-2-fluorobenzene with N,N-dimethylethylenediamine catalyzed by Pd 2 (dba) 3 in the presence of rac-BINAP as the cocatalyst and sodium tert-butoxide as the base in refluxing toluene. Subsequent nucleophilic phosphanylation 28, 29 with KPPh 2 in refluxing 1,4-dioxane produces H[PNN] as colorless crystals in 80% yield. Both H[PNN] and its fluorine precursor were fully characterized by multinuclear NMR spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

Organoaluminium complexes incorporating an amido phosphine chelate with a pendant amine arm

Lee

Liang

2005

Dalton Trans.

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The palladium-catalyzed aryl amination of 1-bromo-2-fluorobenzene with N,N-dimethylethylenediamine quantitatively produces N-(dimethylaminoethyl)-2-fluoroaniline, which subsequently reacts with KPPh2 in 1,4-dioxane to afford N-(dimethylaminoethyl)-2-diphenylphosphinoaniline (H[PNN]). The reactions of trialkylaluminium with H[PNN] in toluene generate the corresponding aluminium dialkyl complexes [PNN]AlR2 (R = Me, Et, i-Bu). The solution NMR spectroscopic and X-ray crystallographic studies are indicative of a trigonal bipyramidal geometry for these aluminium complexes in which the amino nitrogen atom is trans to the phosphorus donor of the [PNN]- ligand. This study presents rare examples of structurally characterized, five-coordinate aluminium hydrocarbyl complexes supported by phosphine-derived ligands.

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“…Similarly, the condensation of diphenylphosphane 5 with 4-chlorobenzonitrile 6 , provided 4-(diphenylphosphanyl)benzonitrile 7 , which upon reduction with LiAlH 4 resulted in amine 8 . Phosphine oxidation of the amine 8 with hydrogen peroxide afforded the second GAP-equipped benzylamine 9 or “dppBnNH 2 ” ( Scheme 1 ) (Hingst et al, 1998 ; Janssen et al, 2009 ). The protection of cinnamic acids with dppBnNH 2 was both facile and quantitative compared to dppBnOH.…”

Section: Resultsmentioning

confidence: 99%

Hypervalent Iodine (III) Catalyzed Regio- and Diastereoselective Aminochlorination of Tailored Electron Deficient Olefins via GAP Chemistry

et al. 2020

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Herein, we report a protocol for highly efficient hypervalent iodine (III) mediated, group-assisted purification (GAP) method for the regioselectivities and stereoselective aminochlorination of electron-deficient olefins. A series of vicinal chloramines with multifunctionalities were acquired in moderate to excellent yields (45-94%), by merely mixing the GAP auxiliary-anchored substrates with dichloramine T and tosylamide as chlorine/nitrogen sources and iodobenzene diacetate as a catalyst. The vicinal chloramines were obtained without any column chromatographic purification and recrystallization simply by washing the reaction mixture with a minimum amount of common inexpensive solvents and thus avoiding wastage of silica, solvents, time, and labor. The GAP auxiliary is recyclable and reusable. This strategy is easy to handle, cost-effective, greener, sustainable, environmentally benign, and mostly suitable for the syntheses of vicinal haloamines from various electron-deficient alkenes.

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Nucleophilic Phosphanylation of Fluoroaromatic Compounds with Carboxyl, Carboxymethyl, and Aminomethyl Functionalities − an Efficient Synthetic Route to Amphiphilic Arylphosphanes

Cited by 50 publications

References 39 publications

Convenient Synthesis of Cationic Titanium Complexes with Tridentate Cp,N,P-Ligand Framework: FLP-Like Reactivity at the Ti–N Bond and Unexpected Ligand Hydrogenation Reaction

Convenient Synthesis of Cationic Titanium Complexes with Tridentate Cp,N,P-Ligand Framework: FLP-Like Reactivity at the Ti–N Bond and Unexpected Ligand Hydrogenation Reaction

Organoaluminium complexes incorporating an amido phosphine chelate with a pendant amine arm

Hypervalent Iodine (III) Catalyzed Regio- and Diastereoselective Aminochlorination of Tailored Electron Deficient Olefins via GAP Chemistry

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